研究生: |
鄭皓升 Hao-Sheng Cheng |
---|---|
論文名稱: |
高活性非鉑系鎳釕觸媒於鹼性電解質下 電催化析氫與氫氧化反應之研究 Study of high performance non-platinum NiRu catalyst for electrocatalytic hydrogen evolution and oxidation reactions in alkaline electrolyte |
指導教授: |
黃炳照
Bing-Joe Hwang |
口試委員: |
蘇威年
Wei-Nien Su 林昇佃 Shawn D. Lin 王丞浩 Chen-Hao Wang |
學位類別: |
碩士 Master |
系所名稱: |
工程學院 - 化學工程系 Department of Chemical Engineering |
論文出版年: | 2017 |
畢業學年度: | 105 |
語文別: | 中文 |
論文頁數: | 122 |
中文關鍵詞: | 氫氣氧化反應 、氫氣析出反應 、鎳 、釕 、合金 、協同效應 |
外文關鍵詞: | hydrogen oxidation reaction, hydrogen evolution reaction, nickel, ruthenium, alloy, synergistic effect |
相關次數: | 點閱:454 下載:3 |
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本研究利用水熱法(Hydrothermal)合成不同比例之鎳釕雙金屬合金並承載於高表面積碳黑上,進行鹼性燃料電池陽極氫氣氧化反應之探討與鹼性下氫氣析出反應之應用。
利用TEM觀察觸媒顆粒大小分布在2~3 nm之間,並具有良好之分散性,且由X光吸收光譜之結果發現當觸媒中釕金屬之比例越低時,越容易造成金屬聚集,導致合金化程度的下降。本研究中,鎳釕比例為1:1及1:3時有較高之合金程度,表面組成也較為均勻。
在鹼性氫氣氧化反應之機制探討中利用電化學量測一氧化碳剝除實驗,推論鎳釕合金中釕的空軌域較少,其電子密度較飽滿對氫之吸附能降低,以及模擬計算得知鎳釕合金中表面鎳對OH基之吸附能大幅降低,推論協同效應之存在。
本研究成功以尿素調整合成環境以替代DMF合成鎳釕合金觸媒,並保有相當之活性。穩定性測試部分,本實驗使用循環伏安分析加速觸媒老化以比較氫氣氧化反應之穩定性,在經過3000圈老化測試後,活性下降13%。氫氣析出反應則使用定電流方式觀察過電位之變化來分析觸媒的穩定程度,在經過12小時穩定性測試後,過電位僅增加0.08 V。
In this study, the nickel (Ni)-ruthenium (Ru) bimetallic catalysts with different Ni/Ru ratios were successfully loaded on high-surface-area carbon black by using hydrothermal method. The bimetallic Pt-free catalyst shows a Pt-like activity and highly durable in alkaline hydrogen oxidation (HOR)/evolution (HER) reactions.
Through the materials characterization, the particle size distribution for Ni-Ru catalyst was observed as around 2 ~ 3 nm compared to Ru/C which shows around 2 nm. In the results of X-ray absorption spectroscopy the alloy extent of the NixRuy/C catalysts gets increased with increasing Ru content, while particle agglomeration is found by excess Ni content. Higher alloy extent can be found in the Ni/Ru ratio of 1 and 1/3 which leads to more uniform surface composition.
Reaction mechanism of the alkaline HOR has been widely discussed but still debated. Here we combined the experiments and the theoretical computation to propose a synergistic effect for alkaline HOR rather than only electronic effect. The results of CO stripping for Ru-based catalyst evidence the electron transfer from Ni to Ru because of negative shift of onset potential by addition of Ni, in which the electronic effect can be involved to weaken hydrogen binding energy. On the other hand, the computational results show the weakening adsorption of OH group on the Ni-Ru interfacial sites of the alloy surfaces, which may facilitate the Volmer step and enhance HOR performance.
For alkaline HOR/HER, Ni-Ru bimetallic catalyst exhibits an excellent activity as well as competitive performance to commercial Pt catalyst (Pt/C), which attributes to the synergistic effect. Moreover, the stability test for the bimetallic catalyst is much better than the Pt/C catalyst, indicating that the Ni-Ru catalyst has their potential to develop.
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